Journal of Non-Crystalline Solids 357 (2011) 2156–2162

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Journal of Non-Crystalline Solids

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j n o n c r y s o l

Synthesis of sodium silicate-based hydrophilic silica aerogel beads with superior

properties: Effect of heat-treatment
Pradip B. Sarawade a, Jong-Kil Kim b, Askwar Hilonga a, Dang Viet Quang a, Sun Jeong Jeon a, Hee Taik Kim a,⁎
a
Department of Chemical Engineering, Hanyang University, 1271 Sa 3-dong, Sangnok-gu, Ansan-si, Gyeonggi-do 426-791, Republic of Korea
b
E&B Nanotech. Co., Ltd., Ansan, Gyeonggi-do, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: This work demonstrates the synthesis of hydrophilic and hydrophobic high surface area silica aerogel beads
Received 22 November 2010 with a large pore volume. Wet gel silica beads were modified and heat-treated under atmospheric pressure
Received in revised form 10 February 2011 after modification of the surface by trimethychlorosilane (TMCS). The effects of heat treatment on the physical
Available online 21 March 2011
(hydrophobicity) and textural properties (specific surface area, pore volume, and pore size) of silica aerogel
beads were investigated. The results indicated that hydrophobicity of the silica aerogel beads can be
Keywords:
Silica aerogel beads;
maintained up to 400 °C. The hydrophobicity of the silica aerogel beads decreased with increasing
Atmospheric pressure drying (APD); temperature in the range of 200–500 °C, and the beads became completely hydrophilic after heat treatment
Specific surface area; at 500 °C. The specific surface area, cumulative pore volume, and pore size of the silica aerogel beads increased
Heat treatment with increasing temperature. Heating the TMCS modified bead gel at 400 °C for 1 h resulted in silica aerogel
beads with high surface area (769 m2/g), and large cumulative pore volume (3.10 cm3/g). The effects of heat
treatment on the physical and textural properties of silica aerogel beads were investigated by field emission
scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermogravimetric and
differential analysis (TG-DTA), Fourier-transform infrared spectroscopy (FT-IR), and Brunauer, Emmett and
Teller (BET) and BJH nitrogen gas adsorption and desorption methods.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction adsorption (desiccants). Hence current research efforts have endeav-

Silica aerogels are the most highly porous nanostructured
materials in materials science. Their properties include high porosity
(N90%), high specific surface area (500–1000 m2/g), low bulk density
(~0.03 g/cm3), extremely low thermal conductivity (0.005 W/mk),
and low sound velocity (100 m/s) [1,2]. Because of these remarkable
properties, aerogels are ideal candidates for various applications, such
as thermal super-insulators for solar energy systems, refrigerators and
insulated flasks [3], adsorbents, sensors, drug delivery systems, and
even have potential for use in oil-spill clean-ups [4–8].
The normal preparation method for aerogels, which includes
supercritical/subcritical extraction of pore liquid from wet gels, limits
industrial-scale production of these materials. Currently, silica
aerogels are synthesized at an ambient pressure via solvent exchange
and surface modification of wet gels [9]. Previously, it was found that
the one-step solvent exchange surface modification process is suitable
for synthesis of silica aerogel beads at an ambient pressure (APD) [10].
Even though the product obtained through this method has excellent
physical and textural properties, it is generally hydrophobic. These
products have limited applications in various fields, such as moisture
ored to synthesize “hydrophilic” silica aerogel beads while maintain-
ing their superior physical and textural properties.
The present study reports the effects of heating temperature on the
physical/textural properties of relatively transparent synthesized silica
aerogel beads. With increases in heating temperature, we observed
improvements in physical and textural properties including specific
surface area, pore size, and cumulative pore volume. The results obtained
for hydrophilic silica aerogel beads (heat-treated) were compared with
those of hydrophobic silica aerogel beads (TMCS modified-unheated). The
effects of different heat treatments (from 200 to 500 °C) on the physical
(hydrophobicity) and textural (surface area, pore volume, and pore
diameter) properties of the final product were examined. The results were
compared using different characterization techniques, including Fourier
transform infrared spectroscopy (FT-IR), thermogravimetric and differ-
ential analysis (TG-DTA), field-emission scanning electron microscopy
(FE-SEM), transmission electron microscopy (TEM), Brunauer, Emmett
and Teller(BET),andBJHnitrogengasadsorption anddesorption methods.
2. Materials and methods
2.1. Preparation of wet silica gel beads

⁎ Corresponding author. Tel.: +82 31 400 5274; fax: +82 31 500 3579. Industrial-grade sodium silicate solutions (water–glass molar ratio
E-mail address: khtaik@yahoo.com (H.T. Kim). SiO2:Na2O = 3.4) were used to prepare wet silica gel beads. Sodium

0022-3093/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2011.02.022
 P.B. Sarawade et al. / Journal of Non-Crystalline Solids 357 (2011) 2156–2162
Fig. 1. Photograph showing hydrophobicity of the mesoporous silica aerogel beads heat-treated at different temperatures (a) 200 (unheated), (b) 250, (c) 300, (d) 350, (e) 400, and
(f) 500 °C.
silicate was purchased from Shinwoo Materials Co. Ltd., South Korea.
Acetic acid, which was used as an acid catalyst, was purchased from
Showa Chemical Co. Ltd., Japan. The silylating agent used was
trimethychlorosilane (TMCS) from Duksan Chemicals. Initially, silica
sols were prepared by mixing a water–glass solution with oxalic acid
(catalysts) under continuous stirring. Silica wet gel beads were
prepared by ball dropping method (BDM), dropping the silica sol
(pH~4) into a container with kerosene as the upper layer and aqueous
ammonia solution as the bottom layer. The obtained silica wet gel
beads were aged and washed with water. In order to obtain
hydrophobic silica aerogel beads at an ambient pressure, the as-
prepared silica wet gel beads were modified using an ethanol/TMCS/
n-hexane solution via simultaneous solvent exchange and surface
modification process. Descriptions of the formation of silica wet gel
beads, simultaneous solvent exchange, and surface modification
procedure were published previously [10]. To obtain hydrophobic
silica aerogel beads, modified silica wet gel beads were dried at room
temperature (~25 °C) for 24 h and then at 80 °C for 2 h. These drying
Fig. 2. TG/DTA curves of (a) hydrophobic (unheated), and (b) heat-treated at 400 °C
mesoporous silica aerogel beads. The solid black line corresponds to the unheated
sample (TGA), the solid red line corresponds to the heat-treated sample at 500 °C
(TGA), the dotted blue line corresponds to the unheated sample (DTA) and the dotted
green line corresponds to the heat-treated sample at 500 °C (DTA).
2157
procedures reduced shrinkage of the beads. To completely evaporate
the pore liquid, the product was dried at 180 °C for 1 h at an ambient
pressure. In the present study, in order to obtain hydrophilic silica
aerogel beads, the hydrophobic aerogel beads were heated in air at
various temperatures: 200, 250, 300, 350, 400, and 500 °C for 1 h.
2.2. Characterization methods
The textural properties of the modified and heat-treated silica
aerogel beads (packing bed density, porosity, hydrophobicity, hydro-
philicity and water absorption) were measured using the methods
described previously [10]. The following methods were used to
investigate the water absorption capacity of the silica aerogel beads.
Unheated (hydrophobic) and heat-treated (hydrophilic) silica aerogel
beads were crushed to powder, and 10 g of powder was placed on a
polyethylene plate, as polyethylene does not absorb water. Water was
added drop-by-drop to the center of the sample from a burette, and
the mixture was thoroughly kneaded with a spatula after each drop
was added. The dropping and kneading were repeated until the entire
sample became a solid lump of putty. The amount of water added was
recorded and the amount of water absorption was expressed in terms
of ml/g (volume of water absorbed/weight of the sample).
The specific surface area, average pore size, cumulative pore volume,
N2 gas adsorption/desorption isotherms and pore size distributions
(PSDs) of the hydrophobic and hydrophilic silica aerogel beads were
characterized by a BET N2 gas adsorption/desorption apparatus (ASAP
2000, Micromeritics, USA). In particular, the BJH method and desorption
isotherm data were used to calculate the total pore volume and pore size
distributions, respectively [11]. Samples were examined by TG-DTA to
Fig. 3. FT-IR spectra of the silica aerogel beads heat-treated at different temperatures
(a) 200 (unheated), (b) 300, (c) 350, (d) 400, and (f) 500 °C.
2158 P.B. Sarawade et al. / Journal of Non-Crystalline Solids 357 (2011) 2156–2162

Table 1
Effects of heat-treatment on the physical and textural properties of silica aerogel beads prepared by surface modification of silica wet gel beads by TMCS and dried at ambient
pressure (APD).

No. Heating temp. Surface area (m2/g) Packing bed density Pore diameter Pore volume (cm3/g) Porosity Water absorption
(°C) (g/cm3) (nm) (%) (ml/g)
BET method BJH method

1 200 524 ± 32 0.082 ± 0.03 8.64 ± 0.36 2.72 ± 0.20 95.79 ± 0.63 0.103 ± 0.04
2 250 586 ± 30 0.086 ± 0.02 9.13 ± 0.28 2.74 ± 0.25 95.59 ± 0.54 0.108 ± 0.05
3 300 622 ± 44 0.081 ± 0.04 12.61 ± 0.44 2.76 ± 0.26 95.85 ± 0.65 0.123 ± 0.07
4 350 684 ± 27 0.079 ± 0.03 13.65 ± 0.51 2.79 ± 0.19 95.95 ± 0.46 0.146 ± 0.09
5 400 769 ± 41 0.074 ± 0.02 16.31 ± 0.42 3.10 ± 0.21 96.21 ± 0.39 3.261 ± 0.11
6 500 776 ± 32 0.078 ± 0.02 15.42 ± 0.31 3.02 ± 0.24 96.00 ± 0.41 3.174 ± 0.13

study the effect of heating temperature on the silica aerogel beads. FT-IR
was employed to observe the effect of heat treatment on silica surface
alkyl groups (―CH3) using a Perkin-Elmer FT-IR-783 instrument, USA.
For this purpose, as-prepared silica aerogel beads were ground into a
refined powder, mixed with KBr, and pressed to form sample pellets for
FT-IR measurements. Microstructural studies of the aerogel bead
samples were performed using field FE-SEM and TEM (JSM 6700 F, JEOL).
The error in the measurements for % porosity, packing bed density,
and water absorption was calculated as a root mean square (RMS)
using the formula [∑{x − x−}2/4]1/2, where, x and x− represent actual
and mean values respectively. The results reported in this study are
based on the averages of four sets of experiments.
3. Results
3.1. Effect of heat treatment on the properties of the silica aerogel beads
The amount of water absorbed by the heat-treated aerogel beads
was measured to evaluate the effect of heating temperature on the
hydrophobicity of the final product. For this purpose, the as-prepared
hydrophobic silica aerogel bead samples were heated in a furnace in
air at various temperatures (200, 250, 300, 350, 400, and 500 °C) for
1 h. Heat-treated silica aerogel beads were tested by placing them
directly on the water surface as shown in Fig. 1. The increase in weight
was recorded. Silica aerogel beads that were heat-treated below
300 °C do not absorb water and tend to float on the surface (Fig. 1(a)).
Silica aerogel beads that were heat-treated at above 350 °C did absorb
some water and, therefore, were partially submerged below the
surface of the water. Silica aerogel beads that were heat-treated at
400 °C were completely submerged. Further increases in heating
temperature caused the silica aerogel beads to absorb more water and
immediately sink to the bottom of the container. The maximum
temperature up to which the hydrophobic silica aerogel beads
retained hydrophobic behavior was 400 °C; beyond this temperature,
they became hydrophilic.
different temperature in the range of 200 to 500 °C. The peaks centered
at 1070 and 495 cm− 1 correspond to the Si―O―Si bonds and are the
most informative of the silica network structure [13,14]. The broad
absorption peak centered at 3450 cm− 1 and 1630 cm− 1 corresponding
to the O―H absorption band is possibly caused by physically adsorbed
water [15,16]. The strong absorption peaks at 2980, 1360 and 840 cm− 1
correspond to terminal ―CH3 groups, which are attributed to surface
modification by TMCS [17,18]. The peak at 2910 cm− 1 and 1256 cm− 1,
which was present in modified hydrophobic silica aerogel beads,
clearly disappeared after heat treatment at 400 °C. This change
indicated that the attached group (―CH3) becomes oxidized at that
temperature, converting the hydrophobic aerogel beads into its
hydrophilic counterpart. The transition temperatures of the aerogel
beads (hydrophobic to hydrophilic) were determined using TG-DTA
and are shown in Fig. 2.
3.3. Water adsorption studies
Water absorption studies were carried out on unheated and heat-
treated silica aerogel bead powders. The hydrophilic (heat-treated at
400 °C) silica aerogel beads absorbed water greater than 3.26 ml/g.
The unheated (hydrophobic) silica aerogel bead powders had very
low water absorption capacities compared to heated powders. The
results are summarized in Table 1.
3.4. Effect of heat treatment on the textural properties of silica aerogel
beads
The properties (specific surface area, pore volume, pore size, and %
porosity) of unheated and heat-treated silica aerogel beads are
compared in Table 1. Additionally, the specific surface areas of the
silica aerogel beads with respect to different heat treatments are
shown in Fig. 4. It was observed that the specific surface area
increased from 524 to 776 m2/g with increasing temperature within
the range of 200–500 °C. The cumulative pore volume and average

3.2. TG-DTA and FT-IR spectra analyses 800

BET specific surface area (m2/g)

The TG-DTA results for hydrophobic silica aerogel beads were 750
compared with those of heat-treated silica aerogel beads. Fig. 2(a) and
(b) shows the TG-DTA analyses of the TMCS-modified for unheated 700
and heat-treated samples, respectively. The curves clearly show that
the hydrophobic TMCS-modified silica aerogel beads exhibited 650
negligible weight loss up to 390 °C, beyond which the aerogel beads
underwent a significant weight loss. This decrease in weight is due to 600
the oxidation of surface methyl groups, which are clearly seen by
sharp exothermic peaks in the DTA curve when the temperature 550
is raised above 390 °C [12]. On the other hand, heat-treated silica
500
aerogel beads showed continuous weight loss with increasing 100 200 300 400 500 600
temperature (Fig. 2(b)).
Heating temperature (°C)
The effect of heat treatment on hydrophobic silica aerogel beads
was observed by using FT-IR. Fig. 3 shows the FT-IR spectra of Fig. 4. Variation of BET specific surface area with the increase in heating temperature
hydrophobic and heat-treated silica aerogel bead samples in air at from 200 to 500 °C. Line is drawn as guides for the eye.
 P.B. Sarawade et al. / Journal of Non-Crystalline Solids 357 (2011) 2156–2162
pore diameter increased slightly with increasing temperature from
200 to 400 °C (Table 1). Further increases in temperature resulted in a
slight decrease in pore diameter and cumulative pore volume whereas
packing bed density decreased with increasing temperature up to
400 °C. The decreases in packing bed density cause the % porosity to
increase. Further, upon increasing temperature, there was a slight
increase in packing bed density and hence % porosity decreased.
N2 adsorption and desorption isotherms and pore size distribution
of the silica aerogel beads were studied to determine the effect of heat
treatment on the nature of the pores in the aerogel bead network.
Fig. 5 shows N2 adsorption/desorption isotherms of unheated and
heat-treated aerogel beads. The unheated and heat-treated silica
aerogel beads showed similar isotherms and are comparable to
supercritical/ambient pressure dried silica aerogels (H1 type) [19,20],
although they have a relatively low surface area and pore size. H1 type
hysteresis loops indicate a cylindrical pore [21]. Large hysteresis loops
indicate the existence of more pores in the silica network. The
physisorption isotherms obtained for all aerogel bead samples
exhibited similar hysteresis loops, which correspond to the charac-
teristic features of mesoporous materials (Type IV isotherms) [22,23].
The absorption volumes of each aerogel bead sample differed and
increased with increasing temperature (200–400 °C). The increase in
pore volume was associated with the removal of residual organic
components and ―CH3 groups from the bead gel.
Fig. 6 shows the pore size distribution (PSDs) curves of unheated
and heat-treated silica aerogel beads. The unheated aerogel beads had
a broad pore size distribution with an average diameter of 8.64 nm.
The heat-treated aerogel beads had a broader pore size distribution
with an average diameter of 16.31 nm. After heating the modified
samples at 400 °C the peak pore diameter shifted to a higher value. It
should be noted that the samples (modified and heat-treated)
reported in this study showed a pronounced peak in the mesopore
region (2–50 nm) [24], indicating that the aerogel beads maintained
mesoporosity even after high temperature heat treatment.
3.5. FE-SEM and TEM studies
The effect of heat treatment on the microstructure of the silica
aerogel beads was observed by FE-SEM and TEM. Fig. 7 shows SEM
micrographs of the unheated silica aerogel beads and beads that
were heat-treated at different temperatures (250–500 °C). It can be
Fig. 5. N2 adsorption/desorption isotherms of the silica aerogel beads heat-treated at
different temperatures (a) 200 (unheated), (b) 300, (c) 350, (d) 400, and (f) 500 °C. N2
adsorption/desorption data were calculated by BJH method. Lines are drawn as guides
for the eye.
2159
Fig. 6. Cumulative pore size distributions of the silica aerogel beads heat-treated at
different temperatures (a) 200 (unheated), (b) 300, (c) 350, (d) 400, and (f) 500 °C.
Pore size distribution data were calculated by BJH method. Lines are drawn as guides for
the eye.
seen that particle size slightly decreased when the heat treatment
temperature was increased. The pore size increased after heat
treatment at 250–400 °C. The TMCS modified aerogel beads that
were dried at 200 °C (unheated) appeared to have larger spheres and
smaller pore sizes in their structure (Fig. 7(a)). The aerogel beads that
were heat-treated at 400 °C appeared to have spheres that are small
and uniform in size. The pore size for the heat-treated aerogel bead
was wider than its unheated counterpart. In addition a more uniform
pore size distribution was obtained when silica aerogel beads were
heat-treated at 400 °C (Fig. 7(e)). However, a more dense silica
structure can be observed when samples were heat-treated at 500 °C
(Fig. 7(d)). Fig. 8 shows representative TEM micrographs of unheated
(200 °C) and heat-treated (400 °C) TMCS modified silica aerogel bead
samples. Unheated silica aerogel beads showed porous silica network
microstructures with irregular pore size. On the other hand, the
sample modified with TMCS and heat-treated at 400 °C exhibited a
highly porous sponge-like silica network microstructure with a
uniform pore size distribution in the range of 8–17 nm. The surface
morphology observed by TEM for the heat-treated aerogel beads
was more uniform and had a smaller particle size than the unheated
aerogel bead.
4. Discussion
A silanol group (Si―OH) on the silica aerogel bead surface is
responsible for irreversible shrinkage of the gel while drying at an
ambient pressure because the surface silanol groups undergo
condensation reactions, therefore forming new siloxane bonds
between the adjacent silica clusters [25]. Elimination of capillary
pressure is very important to obtain highly porous silica gel
structures [26]. Highly porous silica gel structures are usually
prepared by supercritical drying of the wet gel, thereby avoiding
capillary stress and drying shrinkage as well as network collapse.
Highly porous silica gel structure, in contrast, can be obtained at an
ambient pressure. Capillary pressure can be reduced during drying by
modifying the silica gel surface with non-polar alkyl groups by
replacing the H atom in Si―OH. Therefore, to reduce irreversible
shrinkage of hydrogel beads during drying, we modified the surfaces
of gel beads using tri-methyl groups (contributed by TMCS) via
simultaneous solvent exchange and surface modification process
using ethanol/TMCS/n-hexane solution. One-step solvent exchange
2160 P.B. Sarawade et al. / Journal of Non-Crystalline Solids 357 (2011) 2156–2162

a b

c d

e f

Fig. 7. FE-SEM micrograph of the silica aerogel beads heat-treated at different temperatures (a) 200 (unheated), (b) 250, (c) 300, (d) 350, (e) 400, and (f) 500 °C.

surface modification was simultaneously executed by the reaction of
ethanol/TMCS/n-hexane with hydrogel beads. TMCS reacts with pore
water and silanol groups on the surfaces of gel beads, while the
ethanol reacts with TMCS so as to decrease the reaction rate of TMCS
with pore water. It should be noted that the reaction between TMCS
and the pore water is so rapid that ethanol is not added cracking of the
beads may occur. A more detailed explanation for the mechanism of
simultaneous solvent exchange and surface modification process for
silica wet gel beads is reported elsewhere [10].
Chemical and microstructural transformations took place upon
heat treatment of the silica aerogel beads, which consequently
induced changes in the pore structure properties (pore size and
pore volume) of the beads. It was previously reported that low density
silica aerogel beads with high BET surface area and large pore volume
were obtained by modification of wet silica gel beads and drying at an
ambient pressure [10], but these beads were hydrophobic. Therefore,
with the intension of obtaining hydrophilic silica aerogel beads with
good physical and textural properties (large pore size, and high pore
volume), we heat-treated surface modified hydrophobic silica aerogel
beads at different temperatures ranging from 200 to 500 °C. As shown
in Fig. 1, the aerogel beads heat-treated below 300 °C did not absorb
water, whereas aerogel beads heat-treated above 350 °C absorbed
some water and would partially submerge into the water. Beads heat-
treated at 400 °C absorbed more water and completely sank into the
water. This was due to the fact that at this temperature in the range
350–400 °C, there was slow removal of the surface methyl groups
(―CH3) and residual organic components. Initially, the small losses in
weight observed in TGA graphs up to a temperature of 180 °C were
due to the evaporation of absorbed water. The sharp exothermic
peaks observed in the DTA curve when the temperature was raised
above 390 °C were due to the oxidation of the surface methyl groups
(―CH3). Heat-treated silica aerogel beads showed a continuous
 P.B. Sarawade et al. / Journal of Non-Crystalline Solids 357 (2011) 2156–2162
weight loss with the increase in temperature (Fig. 2 (b)). The TG-DTA
results obtained for heat-treated silica aerogel beads are comparable
to that of a typical hydrophilic silica gel/powder [15] and indicate that
heat-treated silica aerogel beads are hydrophilic. Water absorption
results showed that less water was absorbed by unheated hydropho-
bic silica aerogel beads which was attributed to its hydrophobic
nature. Unheated silica aerogel beads have surface alkyl groups that
repel water molecules and result in a lower amount of water absorbed
as shown in Table 1. Heat-treated silica aerogel beads absorbed more
water molecules, likely due to the loss of surface alkyl groups with
increasing temperature [27].
The main effect of heat treatment on the hydrophobic silica
aerogel beads is to reduce/remove the surface hydrophobic alkyl
groups, which can be seen in the FT-IR spectra (Fig. 3). The infrared
absorbance spectra for the hydrophobic (unheated) and hydrophilic
(heat-treated) silica aerogel beads revealed the hydrophobic and
hydrophilic surface characters of the synthesized silica aerogel
beads, as seen in Fig. 3. Overtones of Si―OH-stretching vibrations at
approximately 3450 cm− 1 indicated that the bead gel structure is a
background peak caused by KBr that was added for measurements. At
approximately 1630 cm− 1, a H―OH peak is visible that probably
represents the highly porous and hydrophilic silica matrix, which
easily absorbs water from the air [28]. As shown in Fig. 3, the decrease
in peak intensity of ―CH3 groups, which is observed at 2980 cm− 1,
1360 cm− 1 and 840 cm− 1, is due to the removal of surface alkyl
groups (―CH3) with increasing temperature up to 350 °C. With an
increase in the heating temperature, the peaks at 2980 cm− 1,
1360 cm− 1 and 840 cm− 1 completely disappeared after heat treat-
ment at 400 °C because surface alkyl groups were oxidized, which was
confirmed by TG-DTA results and is shown in Fig. 2.
The BET specific surface area, cumulative pore volume, and
average pore diameter increased slightly with increasing temperature
from 200 to 500 °C (Fig. 4, Table 1). When the silica aerogel was
heated at high temperature its particle size (particle diameter)
decreased while the pore size increased. Hence an increase in pore
size, internal pore volume, and pore surface may occur. Consequently,
the total pore volume and the total specific surface area increase. This
Fig. 8. TEM micrograph (low and high magnification) of (a) unheated TMCS modified silica aerogel beads together with (b) heat-treated silica aerogel beads at 400 °C.
2161
observation is consistent with another report that the specific surface
area increases with a decrease in particle diameter and an increase in
pore diameter after heating the modified gel above 200 °C [15,29,30].
In addition, the pore size and the pore volume increased with
increasing temperature (Table 1). The increase in total pore volume
can be attributed to the removal of residual solvent (water) and
the oxidation of organic groups (―CH3) at high temperature (above
400 °C) as shown in the TG-DTA graph (Fig. 2), which may create
more micro and meospore surface area and hence increase total
pore volume. The decrease in packing bed density of the silica
aerogel beads with increasing temperature up to 400 °C was
attributed to weight loss caused by the removal of absorbed water
and organic groups. The increase in packing bed density at 500 °C
was attributed to the collapse of micro and meso pores caused by
bead gel densification [29].
From the N2 adsorption and desorption isotherms shown in Fig. 5,
the amount of N2 gas absorbed increased with increasing heating
temperature, which is related to the total pore volume. The total pore
volume of the silica aerogel beads increased with increases in heating
temperature due to the removal of residual solvent (water/hexane)
and the oxidation of organic groups. In addition, the larger hysteresis
loops indicated the existence of more pores of restricted access.
The limited N2 uptake at low relative pressures (b0.1) indicates the
existence of mesoporous structures [31,32]. The physisorption
isotherms obtained for all aerogel bead samples exhibited hysteresis
loops which corresponded to the characteristic features of mesopor-
ous materials (Type IV isotherms). From the pore size distribution
studies shown in Fig. 6 it was found that the unheated samples have a
smaller pore size distribution (~9 nm) whereas the heat-treated
samples showed a wider pore size distribution of around 17 nm. The
shifting of peak pore diameter towards a higher value is due to the
removal of residual organic compounds and ―CH3 groups from the
hydrophobic silica aerogel beads.
Generally, modified aerogels have a highly porous, sponge-like
structure with spherical silica particles due to reversible shrinkage
(spring back phenomenon) that takes place during drying, which is a
consequence of organic modification of tri-methyl groups on the silica
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Acknowledgement

This work was supported by the research fund of Hanyang

University (HY-2010-N).